Caesium
Caesium (IUPAC spelling6) (also spelled cesium in American English)1 is a chemical element with the symbol Cs and atomic number 55. It is a soft, silvery-golden alkali metal with a melting point of 28.5 °C (83.3 °F), which makes it one of only five elemental metals that are liquid at or near room temperature.2 Caesium has physical and chemical properties similar to those of Rubidium and Potassium. The most reactive of all metals, it is pyrophoric and reacts with water even at −116 °C (−177 °F). It is the least electronegative element, with a value of 0.79 on the Pauling scale. It has only one stable isotope, caesium-133. Caesium is mined mostly from pollucite, while the radioisotopes, especially caesium-137, a fission product, are extracted from waste produced by nuclear reactors. The German chemist Robert Bunsen and physicist Gustav Kirchhoff discovered caesium in 1860 by the newly developed method of flame spectroscopy. The first small-scale applications for caesium were as a "getter" in vacuum tubes and in photoelectric cells. In 1967, acting on Einstein's proof that the speed of light is the most constant dimension in the universe, the International System of Units used two specific wave counts from an emission spectrum of caesium-133 to co-define the second and the metre. Since then, caesium has been widely used in highly accurate atomic clocks. Since the 1990s, the largest application of the element has been as caesium formate for drilling fluids, but it has a range of applications in the production of electricity, in electronics, and in chemistry. The radioactive isotope caesium-137 has a half-life of about 30 years and is used in medical applications, industrial gauges, and hydrology. Nonradioactive caesium compounds are only mildly toxic, but the pure metal's tendency to react explosively with water means that caesium is considered a hazardous material, and the radioisotopes present a significant health and ecological hazard in the environment. Characteristics Physical properties Caesium is the softest element (it has a hardness of 0.2 Mohs). It is a very ductile, pale metal, which darkens in the presence of trace amounts of oxygen.111213 When in the presence of mineral oil (where it is best kept during transport), it loses its metallic lustre and takes on a duller, grey appearance. It has a melting point of 28.5 °C (83.3 °F), making it one of the few elemental metals that are liquid near room temperature. Mercury is the only elemental metal with a known melting point lower than caesium.315 In addition, the metal has a rather low boiling point, 641 °C (1,186 °F), the lowest of all metals other than mercury.16 Its compounds burn with a blue1718 or violet18 colour. Caesium forms alloys with the other alkali metals, gold, and mercury (amalgams). At temperatures below 650 °C (1,202 °F), it does not alloy with cobalt, iron, molybdenum, nickel, platinum, tantalum, or tungsten. It forms well-defined intermetallic compounds with antimony, gallium, indium, and thorium, which are photosensitive.11 It mixes with all the other alkali metals (except lithium); the alloy with a molar distribution of 41% caesium, 47% potassium, and 12% sodium has the lowest melting point of any known metal alloy, at −78 °C (−108 °F).1519 A few amalgams have been studied: CsHg2 is black with a purple metallic lustre, while CsHg is golden-coloured, also with a metallic lustre.20 The golden colour of caesium comes from the decreasing frequency of light required to excite electrons of the alkali metals as the group is descended. For lithium through rubidium this frequency is in the ultraviolet, but for caesium it enters the blue–violet end of the spectrum; in other words, the plasmonic frequency of the alkali metals becomes lower from lithium to caesium. Thus caesium transmits and partially absorbs violet light preferentially while other colours (having lower frequency) are reflected; hence it appears yellowish.21 History In 1860, Robert Bunsen and Gustav Kirchhoff discovered caesium in the mineral water from Dürkheim, Germany. Because of the bright blue lines in the emission spectrum, they derived the name from the Latin word caesius, meaning sky-blue.6676869 Caesium was the first element to be discovered with a spectroscope, which had been invented by Bunsen and Kirchhoff only a year previously.15 To obtain a pure sample of caesium, 44,000 litres (9,700 imp gal; 12,000 US gal) of mineral water had to be evaporated to yield 240 kilograms (530 lb) of concentrated salt solution. The alkaline earth metals were precipitated either as sulfates or oxalates, leaving the alkali metal in the solution. After conversion to the nitrates and extraction with ethanol, a sodium-free mixture was obtained. From this mixture, the lithium was precipitated by ammonium carbonate. Potassium, rubidium, and caesium form insoluble salts with chloroplatinic acid, but these salts show a slight difference in solubility in hot water, and the less-soluble caesium and rubidium hexachloroplatinate ((Cs,Rb)2PtCl6) were obtained by fractional crystallization. After reduction of the hexachloroplatinate with hydrogen, caesium and rubidium were separated by the difference in solubility of their carbonates in alcohol. The process yielded 9.2 grams (0.32 oz) of rubidium chloride and 7.3 grams (0.26 oz) of caesium chloride from the initial 44,000 litres of mineral water.68 From the caesium chloride, the two scientists estimated the atomic weight of the new element at 123.35 (compared to the currently accepted one of 132.9).68 They tried to generate elemental caesium by electrolysis of molten caesium chloride, but instead of a metal, they obtained a blue homogeneous substance which "neither under the naked eye nor under the microscope showed the slightest trace of metallic substance"; as a result, they assigned it as a subchloride (Cs 2Cl). In reality, the product was probably a colloidal mixture of the metal and caesium chloride.70 The electrolysis of the aqueous solution of chloride with a mercury cathode produced a caesium amalgam which readily decomposed under the aqueous conditions.68 The pure metal was eventually isolated by the German chemist Carl Setterberg while working on his doctorate with Kekulé and Bunsen.69 In 1882, he produced caesium metal by electrolysing caesium cyanide, avoiding the problems with the chloride.71 Historically, the most important use for caesium has been in research and development, primarily in chemical and electrical fields. Very few applications existed for caesium until the 1920s, when it came into use in radio vacuum tubes, where it had two functions; as a getter, it removed excess oxygen after manufacture, and as a coating on the heated cathode, it increased the electrical conductivity. Caesium was not recognized as a high-performance industrial metal until the 1950s.72 Applications for nonradioactive caesium included photoelectric cells, photomultiplier tubes, optical components of infrared spectrophotometers, catalysts for several organic reactions, crystals for scintillation counters, and in magnetohydrodynamic power generators.11 Caesium also was, and still is, used as a source of positive ions in secondary ion mass spectrometry (SIMS). Since 1967, the International System of Measurements has based the primary unit of time, the second, on the properties of caesium. The International System of Units (SI) defines the second as the duration of 9,192,631,770 cycles at the microwave frequency of the spectral line corresponding to the transition between two hyperfine energy levels of the ground state of caesium-133.73 The 13th General Conference on Weights and Measures of 1967 defined a second as: "the duration of 9,192,631,770 cycles of microwave light absorbed or emitted by the hyperfine transition of caesium-133 atoms in their ground state undisturbed by external fields".